RT Journal Article
T1 Two Copper-Carbenes from One Diazo Compound
A1 Álvarez, María
A1 Besora, María
A1 Molina González, Francisco
A1 Maseras, Feliu
A1 Rodríguez Belderraín, Tomás
A1 Pérez Romero, Pedro José
AB Many transition-metal complexes MLn decompose diazo compounds N2-CR1R2 generating metal-carbenes LnM-CR1R2 which transfer the carbene group to other substrates, constituting an important tool in organic synthesis. All previous reports have shown that the CR1R2 fragment at the metal-carbene remains intact from the parent diazo compound. Herein we report the detection and isolation of a monosubstituted copper carbene where the CR1R2 ligand has undergone a modification from the initial diazo reagent. When TpMsCu(THF) (TpMs = hydrotris(3-mesityl)pyrazolylborate ligand) was reacted with N,N-diethyl diazoacetamide [N2-C(H)(CONEt2)], the stable copper carbene TpMsCu-C(H)(NEt2) was isolated, resulting from a decarbonylation process, with carbon monoxide being trapped as TpMsCu(CO). The simultaneous observation of products derived from the intramolecular carbene insertion reaction into C–H bonds demonstrates that the expected TpMsCu-C(H)(CONEt2) complex is also formed. Experimental data, DFT calculations, and microkinetic models allow us to propose that the latter undergoes CO loss en route to the former.
PB American Chemical Society
SN 0002-7863
SN 1520-5126 (electrónico)
YR 2021
FD 2021-03
LK http://hdl.handle.net/10272/19704
UL http://hdl.handle.net/10272/19704
LA eng
NO Álvarez, M., Besora, M., Molina, F., Maseras, F., Belderrain, T. R., & Pérez, P. J. (2021). Two Copper-Carbenes from One Diazo Compound. Journal of the American Chemical Society, 143(12), 4837–4843. https://doi.org/10.1021/jacs.1c01483
NO Funding for open access charge: Universidad de Huelva / CBUA
NO Funding for open access charge: Universidad de Huelva / CBUAWe dedicate this work to the memory of Professor VictorRiera, one of the pioneers of organometallic chemistry inSpain. We acknowledge financial support from the Ministeriode Ciencia e Innovación (CTQ2017-82893-C2-1-R, CTQ2017-87792-R, P. O. Feder UHU-1260216 and P. O. Feder UHU-1254043, and Red Intecat CTQ2016-81923-REDC)
DS Repositorio Institucional de la Universidad de Huelva
RD 15 jun 2026